US4113660A - Production of shaped catalysts or carriers comprising titanium oxides - Google Patents

Production of shaped catalysts or carriers comprising titanium oxides Download PDF

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US4113660A
US4113660A US05/753,323 US75332376A US4113660A US 4113660 A US4113660 A US 4113660A US 75332376 A US75332376 A US 75332376A US 4113660 A US4113660 A US 4113660A
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metatitanic acid
titanium oxide
process according
weight
catalyst
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Kazunobu Abe
Hiroaki Rikimaru
Iwao Yamazaki
Hiroshi Hasegawa
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Sakai Chemical Industry Co Ltd
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Sakai Chemical Industry Co Ltd
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Priority claimed from JP50154606A external-priority patent/JPS5277890A/ja
Priority claimed from JP8942976A external-priority patent/JPS5314188A/ja
Priority claimed from JP10135076A external-priority patent/JPS5326290A/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst

Definitions

  • the present invention relates to production of shaped catalysts or carriers mainly comprising titanium oxide.
  • catalysts or carriers comprising titanium oxide as the main ingredient there are widely known various compositions.
  • various compositions for example, shaped products of metal oxide mixtures comprising V, Ti, Cu, Zn, Sn, Pb, Fe, P, Cr, Co and Ni (Japanese Patent Publication (unexamined) No. 122473/1974 ), comprising Ti and Mo (Japanese Patent Publication (unexamined) No. 89291/1975 ) and comprising Ti and Ce (Japanese Patent Publication (unexamined) No. 23472/1976) have been reported as useful catalysts for elimination of nitrogen oxides from gases containing them by the use of ammonia as a reducing agent. Further, in Japanese Patent Publication (unexamined) No.
  • a shaped carrier comprising titanium oxide has been proposed as an excellent carrier for catalysts to be used for elimination of nitrogen oxides from gases containing them.
  • German Patent Offenlegungsschrift No. 2,534,281 a catalyst comprising V 2 O 5 carried on titanium oxide is described as useful in the production of phthalic anhydride from o-xylene by oxidation.
  • Uma. R has reported in Proc. Indian. Natl. Sci. Acad. Part A, 1975, 41, (1) that a catalyst comprising ZnO-TiO 2 is useful in dehydration reaction of isopropanol to obtain acetone.
  • Katalititcheskie Svoitva Veshestv there has been proposed some catalyst compositions titanium oxide as the main ingredient.
  • a shaped product having a large mechanical strength is hardly obtainable by a conventional shaping procedure, for instance, extrusion-shaping method or tumbling granulation method. Therefore, it is usually necessary to adopt tablet-shaping, to use a sintering-caking agent (e.g. aluminum powder) on shaping and calcine at 650° to 900° C. (Japanese Patent Publication No. 43553/1973 ), or to calcine at 800° to 1200° C. without using a sintering-caking agent for preparation of a shaped product having a large mechanical strength.
  • a sintering-caking agent e.g. aluminum powder
  • the tabletting pressure must be raised for obtaining a sufficiently large mechanical strength, which diminishes the pore volume and makes the control of the pore structure difficult, so that a catalyst showing a high activity or an excellent selectivity or a carrier exhibiting a sufficient holding effect is not obtainable.
  • boric acid, alumina sol, silica sol or the like is employed as the sintering-caking agent.
  • an amount of approximately 15 parts by weight or more to 1 part by weight of the catalyst or carrier is required in order to obtain a satisfactory mechanical strength for catalyst or carrier.
  • the addition of such a large amount of boric acid can not afford a catalyst having a high activity or a carrier showing a sufficient holding effect, because the boric acid added is converted into a glassy material, which blocks pores of titanium oxide or covers the active surface of the catalytically active substance.
  • silica sol or alumina sol a sufficient mechanical strength is not obtainable, and the characteristic properties of the produced catalyst mainly comprising titanium oxide may be sometimes changed.
  • the remarkable crystallization of titanium oxide occurs so that the same defects as seen in the first method is produced.
  • the calcination may be effected at a higher temperature, i.e. from 800° to 1200° C.
  • a vanadium-titanium catalyst having an excellent wearing resistance can be obtained by calcination at 400° to 600° C. in the presence of orthotitanic acid gel.
  • Metatitanic acid sol or gel to be used in the present invention acts efficiently as a binder for titanium oxide to afford a better effect, compared with orthotitanic acid gel. Further, metatitanic acid sol or gel can be prepared more easily and economically with lower cost than orthotitanic acid gel.
  • a certain amount e.g. not more than about 30 % by weight
  • silica sol, clay, titanium sulfate or ceramic fiber e.g., a certain amount (e.g. not more than about 30 % by weight) of silica sol, clay, titanium sulfate or ceramic fiber, a small amount (e.g. not more than about 5 % by weight) of a vanadium compound, carbon, a borate, a silicate or a phosphate may be incorporated into the starting composition to obtain a catalyst or carrier having a desired mechanical strength without substantial deterioration of the characteristic properties of the catalyst or carrier.
  • silica sol or titanium sulfate may be further incorporated in addition to metatitanic acid sol or gel in order to increase the adhesion strength.
  • the catalyst or carrier obtained according to the invention which comprises mainly titanium oxide may be used for various uses. It is particularly suitable for the use as a catalyst or carrier for elimination of nitrogen oxides using ammonia as a reducing agent.
  • metatitanic acid sol and/or gel To a starting material mainly comprising metatitanic acid, previously prepared metatitanic acid sol and/or gel are added, or alternatively a deflocculation agent for metatitanic acid or both a deflocculation agent and a gelation agent are added to cause deflocculation or gelation of all or a part of metatitanic acid in the composition, whereby the content of metatitanic acid sol and/or gel is made to 1 to 100 % by weight (as titanium oxide) based on the weight of the catalyst or carrier.
  • At least one of vanadium compounds, carbon, borates, silicates and phosphates and/or at least one of titanium sulfate, silica sol, clay and glass fiber are incorporated in amounts within the above mentioned ranges.
  • the resultant mixture is subjected to spray drying or adjustment of water content in the starting material and shaping by an optional shaping procedure (preferably extrusion), followed by calcination to obtain a catalyst or carrier.
  • a shaping-promoting agent such as fine crystalline cellulose (e.g. avicel) or CMC may be added to the said mixture prior to the shaping.
  • This procedure does not require a pulverization step, which makes the production cost relatively low.
  • the size of the particles constituting the shaped product can not be controlled so that regulation of pore structure is difficult.
  • a starting material mainly comprising powdery titanium oxide previously prepared metatitanic acid sol and/or gel are added to make a content of 1 to 100 % by weight (as titanium oxide) based on the weight of the catalyst or carrier.
  • a catalyst or carrier having a larger mechanical strength is desired, at least one of vanadium compounds, carbon, borates, silicates and phosphates and/or at least one of titanium sulfate, silica sol, clay and glass fiber are incorporated in amounts within the above mentioned ranges.
  • the resulting mixture is then subjected to spray drying or adjustment of water content and shaping by an optional shaping procedure (preferably extrusion), following by calcination to obtain a catalyst or carrier.
  • a shaping-promoting agent as mentioned above may be incorporated into the said mixture prior to the shaping.
  • the size of the particles constituting the shaped product can be controlled, which makes it possible to obtain a catalyst or carrier having a desired structure.
  • Metatitanic acid sol and/or gel are made present in a metatitanic acid-contaning starting material as in Procedure 1, and the resultant mixture is dried and calcined.
  • the calcined product is, after pulverization into powder, shaped using an inorganic binder such as silica sol or alumina sol, if necessary, in the presence of a shaping-promoting agent such as fine crystalline cellulose or CMC by an optional shaping procedure (preferably extrusion or tumbling granulation), dried and calcined to obtain a catalyst or carrier.
  • At least one of vanadium compounds, carbon, borates, silicates and phosphates and/or at least one of titanium sulfate, silica sol, clay and glass fiber may be incorporated in amounts within the above mentioned ranges.
  • the catalyst or carrier obtained by this procedure shows an extremely large mechanical strength under the same shaping conditions in comparison with the case that other titanium oxide powder is shaped with a binder such as silica sol.
  • the size of the particles constituting the shaped product can be controlled, which makes it possible to obtain a catalyst or carrier having a desired pore structure.
  • metatitanic acid sol and/or gel are made present as in Procedure 1, and the resultant mixture is dried and calcined.
  • the calcined product is, after pulverized into powder, shaped using a metatitanic acid sol or gel as a binder, if necessary, together with the above mentioned shaping-promoting agent by an optional shaping procedure (preferably tumbling granulation).
  • the shaped product is dried and calcined to obtain a catalyst or carrier.
  • at least one of vanadium compounds, carbon, borates, silicates and phosphates and/or at least one of titanium sulfate, silica sol, clay and ceramic fibers may be incorporated in amounts within the above mentioned ranges.
  • a catalyst material or the starting material for catalyst in the form of solution, sol, gel or powder and/or a carrier material or the starting material for carrier in the form of solution, sol, gel or powder are added, and metatitanic acid sol and/or gel are further added thereto.
  • the resultant mixture is shaped by an optional shaping procedure, dried and calcined to obtain a shaped catalyst.
  • at least one of vanadium compounds, carbon, borates, silicates and phosphates and/or at least one of titanium sulfate, silica sol, clay and ceramic fiber are incorporated in amounts within the above mentioned ranges.
  • metatitanic acid sol and/or gel and, if necessary, silica sol are added to prepare a suspension, into which a previously shaped inactive material such as cordierite,glasse or ⁇ -alumina is immersed. Then, the inactive material is taken out from the suspension, and after elimination of excess liquid or slurry, subjected to drying and calcination to obtain a shaped catalyst or carrier in which a coating of catalyst or carrier material such as titanium oxide is formed on the inactive material.
  • this procedure is the most suitable for preparation of a shaped catalyst having a complicated structure (e.g honeycomb structure) in which a large mechanical strength can be obtained only with difficulty by an ordinary procedure.
  • titanium oxide there are known three forms, i.e. rutile, brookite and anatase, which are all utilizable as the starting material in the present invention.
  • the catalyst or carrier is used for elimination of nitrogen oxides, the use of the anatase form is preferred.
  • the catalyst or carrier is employed in the catalytic oxidation of butene in a gaseous phase to obtain acetic acid, the use of the rutile form is desirable (Japanese Patent Publication (unexamined) No. 94589/1974 ).
  • Titanium oxide or a substance convertible into titanium oxide on calcination is preferably used in a powder form, because a uniform catalyst can be obtained and the pore distribution and the pore volume as well as the mechanical strength can be adjusted by control of the particle size of the powder.
  • titanium oxide powder which is obtained by incorporating at least one of metatitanic acid sol and metatitanic acid gel into metatitanic acid and subjecting the mixture to drying, calcination and pulverization.
  • the shaped product is advantageous in being not practically contracted on calcination.
  • titanium oxide powder obtained by calcining metatitanic acid at a temperature of 500° C. or lower and subjecting the calcined product to pulverization.
  • the substance convertible into titanium oxide on calcination may be, for instance, a lower oxide of titanium (e.g. Ti 2 O 3 obtained by reducing roasting ilumenite and extracting it by an acid), a volatile titanium compound such as titanium tetrachloride, lower alkyl titanante (e.g. isopropyl titanate), metatitanic acid, orthotitanic acid, etc.
  • a lower oxide of titanium e.g. Ti 2 O 3 obtained by reducing roasting ilumenite and extracting it by an acid
  • a volatile titanium compound such as titanium tetrachloride, lower alkyl titanante (e.g. isopropyl titanate), metatitanic acid, orthotitanic acid, etc.
  • metatitanic acid is the most preferable in respect of convenience in handling and production cost.
  • the metatitanic acid sol or gel serves as a binder combining titanium oxide, the catalyst material, the inactive material and the carrier material firmly.
  • the combination between the catalyst material and the carrier material thus attained by the metatitanic acid sol or gel makes an excellent holding effect which is hardly obtained by mere admixture of the catalyst material and the carrier material.
  • the metatitanic acid sol or gel also serves, in the carrier of the invention, as a binder combining titanium oxide, the other carrier material and the inactive material firmly.
  • the calcined product containing such a binder shows a large mechanical strength, and the powder obtained by pulverization of such calcined product can afford a shape product showing a small contraction rate and being rich in macropores to prevent cracking at impregnation.
  • the metatitanic acid sol to be used in the invention may be prepared from metatitanic acid (composition: TiO(OH) 2 , 40.4 - 49.0 % by weight; H 2 SO 4 , 2.0 - 3.2 % by weight; H 2 O, 47.8 - 57.6 % by weight) obtained in the course of the production of titanium oxide according to a conventional sulfuric acid process by elimination of sulfuric acid present therein as barium in sulfate and deflocculation of the resulting metatitanic acid with hydrochloric acid, or addition of barium chloride to the said metatitanic acid.
  • the metatitanic acid sol can be converted into a gel form under pH of 1 or higher, preferably 1 to 7.
  • Adjustment of such pH may be effected, for instance, by the use of ammonia.
  • the amount of the metatitanic acid sol or gel to be used in the invention may be 1 to 100 % by weight as titanium oxide to the weight of the catalyst or carrier. In usual, an amount of 5 to 20 % by weight can afford a product having a sufficient quality.
  • Preparation of the metatitanic acid sol or gel may be effected in the starting material comprising metatitanic acid by deflocculating all or a part of it, prior to heating, calcination and shaping.
  • Titanium sulfate as an optional component contributes to the combination between the particles of the carrier or catalyst material and the substrate.
  • the titanium sulfate may be, for example, titanium oxysulfate, titanous sulfate or titanic sulfate or an aqueous solution thereof.
  • the amount of the titanium sulfate to be used is preferably 1 to 30 % by weight as titanium oxide to the weight of the catalyst or carrier. When the amount is less than 1 % by weight, a sufficient improvement in strength can not be expected. Even if it is used in an amount of more than 30 % by weight, the binding effect is not much enhanced.
  • Vanadium oxide has a relatively low melting point and can promote the sintering between the particles of the catalyst or carrier material at a temperature which does not make progress the sintering of the catalyst or carrier components such as titanium oxide. Therefore, a carrier having a sufficient mechanical strength and large porosity and surface area, and a catalyst having a satisfactory mechanical strength and showing high activity are obtainable.
  • the vanadium compound may be the one which can be converted into vanadium oxide on calcination. Specific examples are vanadium pentoxide and vanadium sesquioxide. For increasing sufficiently the strength of the shaped product, the vanadium compound is desired to be more uniformly admixed with the starting material for catalyst or carrier such as titanium oxide, and the use of a water-soluble vanadium compound such as ammonium metavanadate, vanadyl sulfate or vanadyl oxalate is preferred.
  • the amount of the vanadium compound to be used is preferably 1 to 5 % by weight as vanadium oxide to the catalyst or carrier such as titanium oxide. When the amount is less than 1 % by weight, a sufficient strength can not be attained. When it is more than 5 % by weight, a satisfactory porosity and surface area or activity can not be obtained, because vanadium oxide acts as a sintering-promoting agent.
  • a borate having a low melting point serves as a sintering-promoting agent.
  • the use of lead borate is most preferred.
  • zinc borate is the most desirable.
  • the amount of the borate to be used is usually from 2 to 5 % by weight to the catalyst or carrier such as titanium oxide. Since the borate having a low melting point also acts as a sintering-promoting agent like vanadium oxide, the amount of the borate added is naturally in direct proportion to the mechanical strength and in inverse proportion to the specific surface area or activity.
  • the addition of carbon brings about an effect for increase of the mechanical strength without reducing the holding effect of the carrier or the activity of the catalyst.
  • the mechanism of this effect is not yet well clarified.
  • the carbon acts as a reducing agent to reduce a part of titanium oxide, and when the thus produced transitory lower metal oxide or the metal is sintered, carbon monoxide or carbon dioxide is generated by combustion of carbon, whereby the space occupied by the carbon at the shaping step is converted into pores.
  • the carbon to be used in the invention may be a carbonaceous material such as fine powder of coke, active carbon or coal, graphite or carbon black.
  • the amount of the carbon to be used is usually from 1 to 5 % by weight to the weight of titanium oxide in the carrier or the catalyst.
  • the specific surface area of the calcined product can be further increased by supplemental silicate-treatment.
  • This phonomenon is based on the preventing effect, exerted by Si(OH) 4 produced by neutralization of the system, to both the growth of the primary particles of TiO 2 and the rutile transition due to calcination.
  • This treatment is particularly preferred in case of the calcination of 700° to 800° C.
  • the amount of the silicate to be used is usually 0.5 to 5.0 % by weight as SiO 2 to the weight of titanium oxide in the carrier or the catalyst.
  • sodium silicate is the most desirable. Depending on the use of the catalyst or the carrier, however, sodium may sometimes act as a catalyst poison. In such case, another silicate may be appropriately selected.
  • the phosphate seems to exert the same effect as the silicate. Probably, the phosphate has an influence upon the crystal lattice of primary particles of TiO 2 constituting the shaped product at the calcination to prevent their growth, which results in increase of the specific surface area and the pore volume and high activity.
  • the phosphate there may be advantageously employed ammonium primary phosphate, ammonium secondary phosphate and ammonium tertiary phosphate.
  • the amount of the phosphate to be used is usually 0.1 to 5 % by weight as P 2 0 5 to the weight of titanium oxide in the catalyst or the carrier.
  • phosphorus may sometimes act as a catalyst poison, and therefore it should be employed with care.
  • the silica sol may be a commercially available colloid solution comprising ultrafine particles of anhydrous silicic acid dispersed in water.
  • the amount of the silica sol to be used is usually from 2 to 30 % by weight as SiO 2 to the weight of the catalyst or carrier. When the amount is less than 2 % by weight, a sufficient effect is not obtainable. When it is more than 30 % by weight, the quality of titanium oxide is frequently deteriorated.
  • the addition of the silica sol increases the effect of the metatitanic acid sol or gel as a binder.
  • sedimentary clay e.g. Kibushi clay, shale
  • the amount to be used is usually from 2 to 30 % by weight to the weight of the catalyst or the carrier.
  • the ceramic fiber may be the one made of a material which does not reduce the catalytic activity and selected from conventional ceramic fibers (e.g. Al 2 0 3 -SiO 2 fiber, ZrO 2 fiber, SiO 2 fiber, glass fiber).
  • the size of the ceramic fiber may be suitably decided depending on the shaping method or the materials for shaping. For example, in case of tumbling granulation method, a fiber diameter of 1 to 20 ⁇ and a fiber length of 10 to 1000 ⁇ are preferred, and in case of the extrusion molding method, a fiber diameter of 1 - 20 ⁇ and a fiber length of 50 - 600 ⁇ are favorable.
  • the amount to be used is usually not more than 30% by weight, and most usually from 0.5 to 30 % by weight to the weight of the catalyst or the carrier.
  • the ceramic fiber serves as an inner-reinforcing agent for the carrier or the catalyst to increase the mechanical strength and the impact strength.
  • glass fiber comprising SiO 2 in 10 - 65 % by weight, Al 2 O 3 in 2 - 6 % by weight, CaO + MgO in 15 - 20 % by weight and Na 2 O + K 2 O in 8 - 12 % by weight is preferred.
  • metatitanic acid sol 8 liters having a solid content of 540 g/l (as titanium oxide) is obtained.
  • metatitanic acid sol 8 liters having a solid content of 540 g/l (as titanium oxide) is obtained.
  • the thus obtained sol is usually employed as dilution.
  • barium chloride (BaCl 2 .2H 2 O) (42 g) is added, and after sufficient stirring and subsequent regulation of water content, the mixture is extruded through an extrusion-shaping machine (diameter of die, 5 mm).
  • the shaped product is dried at 100° C. for 12 hours and then calcined at 600° C. for 3 hours in the air to obtain a shaped titanium oxide carrier in a cylinder form.
  • composition for fluidized bed having a specific surface area of 15.2 m 2 /g, an apparent density of 1.5 g/ml and an average particle size of 55 to 65 ⁇ and showing an angle of repose of 28.1° and a wearing rate of 0.05 %/hr (wearing test: JIS (Japanese Industrial Standard) K1464).
  • metatitanic acid gel 200 g obtained in Example 2
  • sodium silicate (10 g) and vanadyl sulfate 25 g
  • the resulting mixture is treated in the same manner as in Example 3 to obtain a shaped carrier in a cylinder form.
  • Metatitanic acid (0.8 kg as titanium oxide) and aluminum hydroxide (1 kg as aluminum oxide) are mixed together by the aid of a blender, and a dilution of the metatitanic acid sol obtained in Example 1 (200 g/l as titanium oxide) (1 kg) is added thereto.
  • the mixture is well kneaded by the aid of a kneader and, after dried at 120° C. for 12 hours, heated at 600° C. for 3 hours in the air.
  • the heated product is pulverized by a centrifugal pulverizer, from which the screen has been previously taken off.
  • Orthotitanic acid (1 kg as titanium oxide) obtained by neutralization-hydrolysis of titanyl sulfate is calcined at 700° C. for 3 hours and then pulverized by the aid of a centrifugal pulverizing machine without screen to obtain titanium oxide powder.
  • the thus obtained titanium oxide powder is portionwise introduced into a pan pelletizer in which the nuclear substance has been previously charged while spraying a 250 g/l (as titanium oxide) metatitanic acid sol prepared by adding titanous sulfate to the metatitanic acid sol used in Example 6 to effect sphere-shaping.
  • the thus obtained shaped product being 5 mm in average particle size is dried at 100° C. for 12 hours and then calcined at 900° C. for 3 hours to obtain a shaped titanium oxide in sphere form.
  • a metatitanic acid cake (2.5 kg as titanium oxide) is charged in a kneader, and barium chloride (BaCl 2 .2H 2 0) (63 g) is added thereto and kneaded well to cause partial deflocculation of metatitanic acid.
  • the kneaded product is dried at 100° C. for 12 hours and then calcined at 600° C. for 3 hours.
  • the calcined product is pulverized by the aid of a centrifugal pulverizing machine from which the screen is previously taken off.
  • Dried metatitanic acid powder (0.8 kg as titanium oxide) and aluminum hydroxide powder (1 kg as aluminum oxide) are admixed by the aid of a blender, and metatitanic acid sol (150 g/l, 1kg) obtained by diluting the metatitanic acid sol prepared in Example 1, ammonium primary phosphate (30 g) and carbon (20 g) are added thereto.
  • metatitanic acid sol 150 g/l, 1kg obtained by diluting the metatitanic acid sol prepared in Example 1, ammonium primary phosphate (30 g) and carbon (20 g) are added thereto.
  • the mixture is kneaded by the aid of a kneader, dried at 120° C. for 12 hours and then calcined at 700° C. for 3 hours.
  • the calcined product thus obtained is roughly pulverized by the aid of a centrifugal pulverizing machine from which the screen has been previously taken off.
  • the metatitanic acid sol used in Example 9 500 g
  • 20 % silica sol (as SiO 2 ) 300 g
  • the resultant mixture is, after regulation of water content, kneaded by the aid of a kneader, dried at 120° C. for 12 hours and then calcined at 700° C. for 3 hours in the air.
  • the calcined product is pulverized by the aid of a centrifugal pulverizing machine from which the screen has been previously taken off.
  • the metatitanic acid sol used in Example 6 (500 g) is added, and the mixture is, after regulation of water content, kneaded by the aid of a kneader, dried at 120° C. for 12 hours and then calcined at 600° C. for 3 hours in the air.
  • the calcined product is pulverized by the aid of a centrifugal pulverizing machine from which the screen has been previously taken off.
  • shale clay (300 g) and silica fiber being 5 ⁇ in average fiber diameter and 100 ⁇ in average fiber length (30 g) are added and blended well by the aid of a blender, and the resultant mixture is portionwise introduced into a pan pelletizer in which the nuclear substance has been previously charged while spraying the metatitanic acid sol used in Example 9 to effect sphere-shaping.
  • the shaped product being 5 mm in average particle size is dried at 100° C. for 12 hours and then calcined at 600° C. for 3 hours to obtain a shaped titanium oxide carrier in a sphere form.
  • Metatitanic acid (1 kg as titanium oxide) and the metatitanic acid gel used in Example 5 (500 g) are mixed together and, after regulation of water content, kneaded by the aid of a kneader.
  • the resultant mixture is dried at 120° C. for 12 hours and then calcined at 600° C. for 3 hours in the air.
  • the calcined product is pulverized by the aid of a centrifugal pulverizing machine having a screen of 1 mm ⁇ .
  • the silica sol mentioned above (300 g), the metatitanic acid sol used in Example 9 (300 g) and silica fiber being 5 ⁇ in average fiber diameter and 500 ⁇ in average fiber length (40 g) are added, and the mixture is, after regulation of water content, kneaded well by the aid of a kneader and extruded through an extrusion-shaping machine having a die with extrusion hole in a honeycomb form (cell pitch, 5 mm square).
  • the extruded product is uniformly dried at 100° C. for 12 hours and then calcined at 600° C. for 3 hours to obtain a shaped carrier in a honeycomb form with cell pitch of 5 mm square.
  • This operation is repeated 3 times to obtain a shaped product in a honeycomb form coated with titanium oxide in a coating thickness of about 100 ⁇ .
  • the thus obtained shaped product is calcined at 600° C. for 3 hours in the stream of N 2 containing 5 % of H 2 to obtain a shaped carrier in a honeycomb form coated with titanium oxide.
  • This operation is repeated 2 times to obtain a shaped product in a honeycomb form coated with titanium oxide in a coating thickness of about 100 ⁇ .
  • the shaped product is calcined at 600° C. for 3 hours in the air to obtain a shaped carrier in honeycomb form coated with titanium oxide.
  • Each of the carriers obtained in Examples 3, 5, 8, 10, 12 and 13 (200 ml) is immersed for 1 hour in an aqueous solution of vanadium oxalate (200 ml) prepared by dissolving ammonium metavanadate (49 g) in an aqueous solution containing oxalic acid (140 g) and kept at 60° C. Then, the carrier is taken out from the solution, and after elimination of excess liquid, dried at 100° C. for 12 hours, followed by calcination at 450° C. for 3 hours to give a vanadium oxide catalyst.
  • the thus prepared catalyst is charged into a Pyrex glass tube being 50 mm in inner diameter (the outside being warmed) to make an apparent volume of 86 ml, and a gaseous mixture having a composition as shown in Table 1 is introduced therein at 350° C. at a space velocity of 10,000 l/hr (calculated at normal temperature).
  • the nitrogen oxide-eliminating rate is determined according to the following equation, and the results are shown in Table 2: ##EQU1##
  • a mixture of an aqueous solution of vanadyl oxalate (330 ml) containing vanadium pentoxide (50 g), the above mentioned silica sol (240 ml), the metatitanic acid sol used in Example 13 (240 ml) and a suspension (900 ml) containing the pulverized product obtained in Example 8 (300 g) is pulverized and dispersed well in the presence of glass beads.
  • a substrate in a honeycomb form made from cordierite (cell pitch, 5 mm square) 500 ml
  • the substrate is dried at 60° C. for 10 hours and then calcined at 600° C. for 3 hours to obtain a shaped catalyst in a honeycomb form.
  • the pulverized product is portionwise introduced into a pan pelletizer in which the nuclear substance has been previously charged while spraying the metatitanic acid sol (content of titanium oxide, 200 g/l) used in Example 12 to effect sphere-shaping.
  • the thus obtained shaped product of 5 mm in diameter is dried at 100° C. for 12 hours and then calcined at 500° C. for 3 hours to obtain a shaped catalyst in a sphere form.
  • Example 17 The same powder as prepared in Example 17 (1 kg) and glass fiber comprising SiO.sub. 2 in 24 %, Al.sub. 2 O 3 in 3 %, CaO + MgO in 15 % and Na 2 O in 11% (40 g) being 5 ⁇ in average fiber diameter and 100 ⁇ in average fiber length (40 g) are well blended by a blender, and the resultant mixture is portionwise introduced into a pan pelletizer in which the nuclear substance has been previously charged while spraying the metatitanic acid sol used in Example 6 to effect sphere-shaping.
  • the thus obtained shaped product of 5 mm in average particle size is dried at 100° C. for 12 hours and then calcined at 500° C. for 3 hours to obtain a shaped catalyst in a sphere form.
  • Example 17 The same powder as prepared in Example 17 (1 kg), vanadyl sulfate (30 g), ammonium primary phosphate (30 g) and the metatitanic acid sol employed in Example 6 are charged into a kneader and, after regulation of water content, the components are kneaded well.
  • the kneaded product is extruded through an extrusion-shaping machine having a die of 5 mm in diameter, and the extruded product is dried at 100° C. for 12 hours and then calcined at 550° C. for 3 hours to obtain a shaped catalyst in a cylinder form.
  • Synthetic rutile prepared by subjecting ilmenite powder to reducing roasting and then to extraction with an acid (the quality of the titanium oxide component in ilmenite being raised) (1 kg), 20 % alumina sol (as Al 2 O 3 ) (1 kg) and the metatitanic acid gel used in Example 5 (1 kg) are mixed together, and after regulation of water content, the mixture is kneaded well.
  • the kneaded product is extruded through an extrusion-shaping machine having a die of 5 mm in diameter.
  • the shaped product is dried at 100° C. for 12 hours and then calcined at 600° C. for 3 hours in the air to obtain a shaped catalyst in a cylinder form.
  • Metatitanic acid prepared by hydrolysis of titanium tetrachloride under heating (1 kg as titanium oxide), zinc hydroxide gel (1 kg as ZnO) and the metatitanic acid sol obtained by diluting the metatitanic acid sol prepared in Example 6 (1 kg) are mixed together and, after regulation of water content, the mixture is kneaded well.
  • the kneaded product is extruded through an extrusion-shaping machine having a die of 2 mm in diameter.
  • the extruded product is dried at 100° C. for 12 hours and then calcined at 500° C. for 3 hours to obtain a shaped ZnO-TiO.sub. 2 catalyst in a cylinder form.
  • Titanium oxide powder obtained by calcination of metatitanic acid at 600° C. for 3 hours (900 g) and copper oxide powder obtained by calcination of copper nitrate (100 g) are blended under a dry condition by the aid of a blender.
  • the resultant powder mixture is portionwise introduced into a pan pelletizer in which the nuclear substance has been previously charged while spraying the metatitanic acid sol used in Example 6 to obtain a shaped product in a sphere form being 5 mm in average size, which is dried at 100°C. for 12 hours and then calcined at 500°C. for 3 hours to obtain a shaped catalyst.
  • Titanium oxide powder used in Example 22 (1 kg), shale clay (300 g), glass fiber used in Example 12 (30 g), metatitanic acid sol used in Example 6 (500 g), silica sol used in Example 10 (300 g), tungsten oxide (50 g) and uranium oxide powder (100 g) are charged into a kneader, and after regulation of water content, the components are kneaded well.
  • the kneaded product is extruded through an extrusion-shaping machine having a die of 5 mm in diameter.
  • the extruded product is dried at 120° C. for 12 hours and then calcined at 500° C. for 3 hours to obtain a shaped catalyst in a cylinder form.
  • Example 15 Using each of the catalysts obtained in Examples 16, 17, 18, 22 and 23, the same reaction as in Example 15 is carried out, and the nitrogen oxide-eliminating rate is determined. The results are shown in Table 3.
  • the compressive breaking strength (strength to the radius direction in case of a shaped product being in a cylinder form or strength per unit area in axial direction in case of a shaped product being in a honeycomb form), the specific surface area, the micropore volume and the average micropore diameter are measured.
  • the determination of the compressive breaking strength is effected by the use of a Hiya type hardness tester.
  • the specific surface area is determined by the BET method, and the micropore volume and the average micropore diameter are determined by the mercury penetration method.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
US05/753,323 1975-12-23 1976-12-22 Production of shaped catalysts or carriers comprising titanium oxides Expired - Lifetime US4113660A (en)

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JP50154606A JPS5277890A (en) 1975-12-23 1975-12-23 Method of manufacturing carriers
JP50-154606 1975-12-23
JP51-89429 1976-07-26
JP8942976A JPS5314188A (en) 1976-07-26 1976-07-26 Production of catalyst
JP51-101350 1976-08-24
JP10135076A JPS5326290A (en) 1976-08-24 1976-08-24 Production of catalyst

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GB (1) GB1541928A (enrdf_load_stackoverflow)
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US4329260A (en) * 1979-09-24 1982-05-11 Uop Inc. Integral shaped replication supports
US4362651A (en) * 1979-03-22 1982-12-07 Schwarzenbek Eugene F High porosity catalysts
US4388288A (en) * 1980-04-23 1983-06-14 Rhone-Poulenc Industries Preparation of shaped titanium dioxide catalyst/carrier and catalysis of gaseous sulfur compounds therewith
US4410448A (en) * 1981-12-28 1983-10-18 The Standard Oil Company Method for controlling the change in the crush strength of a catalyst particle during finishing calcination
US4499195A (en) * 1982-12-23 1985-02-12 Exxon Research & Engineering Co. Thermally stable mixed oxide gels
US4520124A (en) * 1981-03-19 1985-05-28 Sakai Chemical Industry Co., Ltd. Method for producing a catalytic structure for the reduction of nitrogen oxides
US4537873A (en) * 1982-11-29 1985-08-27 Hitachi, Ltd. Catalyst for catalytic combustion
US4663300A (en) * 1985-12-23 1987-05-05 Uop Inc. Pollution control catalyst
US4725572A (en) * 1985-08-19 1988-02-16 Mitsubishi Jukogyo Kabushiki Kaisha Process for preparing a catalyst for removing nitrogen oxides
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US5002917A (en) * 1988-02-09 1991-03-26 Degussa Aktiengesellschaft Molded articles based on pyrogenically produced titanium dioxide method for their manufacturing and uses
US5051391A (en) * 1988-04-08 1991-09-24 Mitsubishi Jukogyo Kabushiki Kaisha Catalyst filter and method for manufacturing a catalyst filter for treating a combustion exhaust gas
US5100858A (en) * 1988-07-01 1992-03-31 Rhone-Poulenc Chimie Moldable/extrudable titanium dioxide particulates
US5206202A (en) * 1991-07-25 1993-04-27 Corning Incorporated Catalyst device fabricated in situ and method of fabricating the device
US5231067A (en) * 1989-04-27 1993-07-27 Degussa Ag Shaped articles based on pyrogenically produced titanium dioxide, method of their production and their use
US5364984A (en) * 1991-10-01 1994-11-15 Degussa Aktiengesellschaft Process for the preparation of 1,3-propanediol by the hydrogenation of hydroxypropionaldehyde
US5366938A (en) * 1989-04-27 1994-11-22 Degussa Ag Shaped articles based on pyrogenically produced titanium dioxide
US5587136A (en) * 1994-05-10 1996-12-24 Mitsui Mining Co., Ltd. Dry process desulfurization and denitrifcation process
WO1998019786A1 (en) * 1996-11-01 1998-05-14 Lockheed Martin Energy Research Corporation Method for preparing hydrous titanium oxide spherules and other gel forms thereof
US5993763A (en) * 1994-09-07 1999-11-30 Huels Aktiengesellschaft Catalyst and process for decomposing HCN in gases
CN1048192C (zh) * 1995-03-16 2000-01-12 中国石化齐鲁石油化工公司 一种用于从石油和天然气加工过程中产生的硫化氢中回收硫磺的二氧化钛催化剂
US6051198A (en) * 1995-01-05 2000-04-18 Nippon Shokubai Co., Ltd. Catalyst for purifying fumigation exhaust gases and a method of purifying fumigation exhaust gases
WO2000058007A1 (de) * 1999-03-26 2000-10-05 Sachtleben Chemie Gmbh Formkörper aus titandioxid, verfahren zu deren herstellung und deren verwendung
US6217732B1 (en) 1997-09-23 2001-04-17 Abb Business Services Inc. Coated products
US6274763B1 (en) * 1996-11-28 2001-08-14 Consortium für elektrochemische Industrie GmbH Shell catalyst for producing acetic acid by gas phase oxidation of unsaturated C4 -hydrocarbons
US6281385B1 (en) * 1998-05-22 2001-08-28 Consortium für elektrochemische Industrie GmbH Process for preparing acetic acid by gas-phase oxidation of saturated C4-hydrocarbons and their mixtures with unsaturated C4-hydrocarbons
US6297180B1 (en) 1995-02-28 2001-10-02 Studiengesellschaft Kohle Mbh Microporous amorphous mixed metal oxides for shape selective catalysis
US6380128B1 (en) * 1999-10-19 2002-04-30 Korea Hydro & Nuclear Power Co., Ltd. V2O5-based catalyst for removing NOx from flue gas and preparing method therefor
US6419889B1 (en) * 1995-10-09 2002-07-16 Shell Oil Company Catalyst, process of making catalyst and process for converting nitrogen oxide compounds
US6534022B1 (en) 1999-10-15 2003-03-18 Abb Lummus Global, Inc. Conversion of nitrogen oxides in the presence of a catalyst supported on a mesh-like structure
US20030130361A1 (en) * 2000-05-04 2003-07-10 Lednor Peter William Catalyst support and a supported metal catalyst, a process for their preparation, and the use of the catalyst
US6602919B1 (en) 1999-09-17 2003-08-05 Ut-Battelle Llc Method for preparing hydrous zirconium oxide gels and spherules
US6667017B2 (en) 1999-10-15 2003-12-23 Abb Lummus Global, Inc. Process for removing environmentally harmful compounds
EP0934770B1 (en) * 1998-02-03 2004-05-12 Nichias Corporation Catalyst and process for the production thereof
US20040187392A1 (en) * 2003-03-24 2004-09-30 Carbo Ceramics Inc. Titanium dioxide scouring media and mehod of production
US20050031529A1 (en) * 1997-10-15 2005-02-10 Sumitomo Chemical Company, Limited Process for producing chlorine
US20060161256A1 (en) * 2002-09-17 2006-07-20 Gunter Ziegler Anti-infectious, biocompatible titanium coating for implants, and method for the production thereof
US7119039B2 (en) * 2003-03-24 2006-10-10 Carbo Ceramics Inc. Titanium dioxide scouring media and method of production
US20070123594A1 (en) * 2003-09-30 2007-05-31 Dogterom Ronald J Titania supports for fisher-tropsch catalysts
US7678723B2 (en) 2004-09-14 2010-03-16 Carbo Ceramics, Inc. Sintered spherical pellets
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US7828998B2 (en) 2006-07-11 2010-11-09 Carbo Ceramics, Inc. Material having a controlled microstructure, core-shell macrostructure, and method for its fabrication
US20110144406A1 (en) * 2008-08-20 2011-06-16 Mitsuru Masatsugu Catalyst and method for thermal decomposition of organic substance and method for producing such catalyst
US8063000B2 (en) 2006-08-30 2011-11-22 Carbo Ceramics Inc. Low bulk density proppant and methods for producing the same
US8216675B2 (en) 2005-03-01 2012-07-10 Carbo Ceramics Inc. Methods for producing sintered particles from a slurry of an alumina-containing raw material
CN102583522A (zh) * 2012-01-09 2012-07-18 四川华铁钒钛科技股份有限公司 用作催化剂载体的二氧化钛的制备方法
US8663518B2 (en) 2011-12-27 2014-03-04 Tronox Llc Methods of producing a titanium dioxide pigment and improving the processability of titanium dioxide pigment particles
US20140303419A1 (en) * 2011-10-18 2014-10-09 Lanxess Deutschland Gmbh Linear butenes from isobutanol
US20150174558A1 (en) * 2013-12-24 2015-06-25 Denso Corporation Ammonia synthesis catalyst
DE102015102484A1 (de) 2014-02-21 2015-08-27 Sachtleben Chemie Gmbh Katalysatorprecursormaterial auf TiO2-Basis, dessen Herstellung und dessen Verwendung
DE102016110374A1 (de) * 2016-06-06 2017-12-07 Huntsman P&A Germany Gmbh Titandioxid-Sol, Verfahren zu dessen Herstellung und daraus gewonnene Produkte
CN108435153A (zh) * 2018-02-28 2018-08-24 安徽迪诺环保新材料科技有限公司 多孔薄壁scr蜂窝催化剂专用载体及其制备方法和应用
CN110201656A (zh) * 2019-06-10 2019-09-06 西安向阳航天材料股份有限公司 一种二氧化钛基催化剂载体的制备方法
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CN115611606A (zh) * 2022-10-13 2023-01-17 江西环宇工陶技术研究有限公司 一种一次烧成的TiO2光催化陶瓷及其制备方法
CN116769331A (zh) * 2023-05-09 2023-09-19 武汉工程大学 一种基于含磷废水吸附脱磷的颜料级钛白粉制备方法

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US4188365A (en) * 1976-04-16 1980-02-12 Mitsui Petrochemical Industries, Ltd. Process for catalytic vapor phase reduction of nitrogen oxides and catalyst composition used therefor
US4362651A (en) * 1979-03-22 1982-12-07 Schwarzenbek Eugene F High porosity catalysts
US4329260A (en) * 1979-09-24 1982-05-11 Uop Inc. Integral shaped replication supports
US4388288A (en) * 1980-04-23 1983-06-14 Rhone-Poulenc Industries Preparation of shaped titanium dioxide catalyst/carrier and catalysis of gaseous sulfur compounds therewith
US4520124A (en) * 1981-03-19 1985-05-28 Sakai Chemical Industry Co., Ltd. Method for producing a catalytic structure for the reduction of nitrogen oxides
US4410448A (en) * 1981-12-28 1983-10-18 The Standard Oil Company Method for controlling the change in the crush strength of a catalyst particle during finishing calcination
US4537873A (en) * 1982-11-29 1985-08-27 Hitachi, Ltd. Catalyst for catalytic combustion
US4499195A (en) * 1982-12-23 1985-02-12 Exxon Research & Engineering Co. Thermally stable mixed oxide gels
US4769356A (en) * 1985-06-20 1988-09-06 Matsushita Electric Industrial Co., Ltd. Catalyst for purifying exhaust gas
US4725572A (en) * 1985-08-19 1988-02-16 Mitsubishi Jukogyo Kabushiki Kaisha Process for preparing a catalyst for removing nitrogen oxides
US4663300A (en) * 1985-12-23 1987-05-05 Uop Inc. Pollution control catalyst
US4954476A (en) * 1987-01-23 1990-09-04 Siemens Aktiengesellschaft Method of making catalysts from titanium oxide
US4925825A (en) * 1987-12-28 1990-05-15 Babcock-Hitachi Kabushiki Kaisha Catalyst for removing nitrogen oxides
US5002917A (en) * 1988-02-09 1991-03-26 Degussa Aktiengesellschaft Molded articles based on pyrogenically produced titanium dioxide method for their manufacturing and uses
US5051391A (en) * 1988-04-08 1991-09-24 Mitsubishi Jukogyo Kabushiki Kaisha Catalyst filter and method for manufacturing a catalyst filter for treating a combustion exhaust gas
WO1989010176A1 (en) * 1988-04-27 1989-11-02 Ceramic Bonding, Inc. Process for the chemical bonding of heavy metals from sludge in the silicate structure of clays and shales and the manufacture of building and construction materials therewith
US4929586A (en) * 1988-06-09 1990-05-29 W. R. Grace & Co.-Conn. Catalysts for selective catalytic reduction DeNOx technology
US4975256A (en) * 1988-06-09 1990-12-04 W. R. Grace & Co.-Conn. Process using catalysts for selective catalytic reduction denox technology
US5100858A (en) * 1988-07-01 1992-03-31 Rhone-Poulenc Chimie Moldable/extrudable titanium dioxide particulates
US5231067A (en) * 1989-04-27 1993-07-27 Degussa Ag Shaped articles based on pyrogenically produced titanium dioxide, method of their production and their use
US5366938A (en) * 1989-04-27 1994-11-22 Degussa Ag Shaped articles based on pyrogenically produced titanium dioxide
US5206202A (en) * 1991-07-25 1993-04-27 Corning Incorporated Catalyst device fabricated in situ and method of fabricating the device
US5364984A (en) * 1991-10-01 1994-11-15 Degussa Aktiengesellschaft Process for the preparation of 1,3-propanediol by the hydrogenation of hydroxypropionaldehyde
US5587136A (en) * 1994-05-10 1996-12-24 Mitsui Mining Co., Ltd. Dry process desulfurization and denitrifcation process
US5993763A (en) * 1994-09-07 1999-11-30 Huels Aktiengesellschaft Catalyst and process for decomposing HCN in gases
US6051198A (en) * 1995-01-05 2000-04-18 Nippon Shokubai Co., Ltd. Catalyst for purifying fumigation exhaust gases and a method of purifying fumigation exhaust gases
US6297180B1 (en) 1995-02-28 2001-10-02 Studiengesellschaft Kohle Mbh Microporous amorphous mixed metal oxides for shape selective catalysis
US6319876B1 (en) * 1995-02-28 2001-11-20 Studiengesellschaft Kohle Mbh Microporous amorphous mixed metal oxides for form-selective catalysis
CN1048192C (zh) * 1995-03-16 2000-01-12 中国石化齐鲁石油化工公司 一种用于从石油和天然气加工过程中产生的硫化氢中回收硫磺的二氧化钛催化剂
US6419889B1 (en) * 1995-10-09 2002-07-16 Shell Oil Company Catalyst, process of making catalyst and process for converting nitrogen oxide compounds
WO1998019786A1 (en) * 1996-11-01 1998-05-14 Lockheed Martin Energy Research Corporation Method for preparing hydrous titanium oxide spherules and other gel forms thereof
US5821186A (en) * 1996-11-01 1998-10-13 Lockheed Martin Energy Research Corporation Method for preparing hydrous titanium oxide spherules and other gel forms thereof
US6274763B1 (en) * 1996-11-28 2001-08-14 Consortium für elektrochemische Industrie GmbH Shell catalyst for producing acetic acid by gas phase oxidation of unsaturated C4 -hydrocarbons
US6217732B1 (en) 1997-09-23 2001-04-17 Abb Business Services Inc. Coated products
US20050031529A1 (en) * 1997-10-15 2005-02-10 Sumitomo Chemical Company, Limited Process for producing chlorine
EP0934770B1 (en) * 1998-02-03 2004-05-12 Nichias Corporation Catalyst and process for the production thereof
US6281385B1 (en) * 1998-05-22 2001-08-28 Consortium für elektrochemische Industrie GmbH Process for preparing acetic acid by gas-phase oxidation of saturated C4-hydrocarbons and their mixtures with unsaturated C4-hydrocarbons
US6660243B1 (en) 1999-03-26 2003-12-09 Sachtleben Chemie Gmbh Titanium dioxide methods of production
WO2000058007A1 (de) * 1999-03-26 2000-10-05 Sachtleben Chemie Gmbh Formkörper aus titandioxid, verfahren zu deren herstellung und deren verwendung
US6602919B1 (en) 1999-09-17 2003-08-05 Ut-Battelle Llc Method for preparing hydrous zirconium oxide gels and spherules
US6534022B1 (en) 1999-10-15 2003-03-18 Abb Lummus Global, Inc. Conversion of nitrogen oxides in the presence of a catalyst supported on a mesh-like structure
US20030180205A1 (en) * 1999-10-15 2003-09-25 Carlborg Joakim A. Conversion of nitrogen oxides in the presence of a catalyst supported on a mesh-like structure
US6667017B2 (en) 1999-10-15 2003-12-23 Abb Lummus Global, Inc. Process for removing environmentally harmful compounds
US6946107B2 (en) 1999-10-15 2005-09-20 Abb Lummus Global, Inc. Conversion of nitrogen oxides in the presence of a catalyst supported on a mesh-like structure
US6380128B1 (en) * 1999-10-19 2002-04-30 Korea Hydro & Nuclear Power Co., Ltd. V2O5-based catalyst for removing NOx from flue gas and preparing method therefor
US20030130361A1 (en) * 2000-05-04 2003-07-10 Lednor Peter William Catalyst support and a supported metal catalyst, a process for their preparation, and the use of the catalyst
US7906132B2 (en) 2002-09-17 2011-03-15 Biocer-Entwickslung GmbH Anti-infectious, biocompatible titanium coating for implants, and method for the production thereof
US20060161256A1 (en) * 2002-09-17 2006-07-20 Gunter Ziegler Anti-infectious, biocompatible titanium coating for implants, and method for the production thereof
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DE2658569A1 (de) 1977-07-14
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